X-ray Shielding Polyurethanes: Synthesis and Characterization

S. Kiran1, Roy Joseph1,

1
Division of Polymeric Medical Devices, Biomedical Technology Wing, Sree Chitra
Tirunal Institute for Medical Sciences and Technology, Trivandrum, Kerala, India

Corresponding author Roy Joseph, . E-mail: rjoseph1965@rediffmail.com

Received 10 October 2016, Accepted 20 November 2016.

Abstract

Synthesis and characterization of X-ray shielding thermoplastic polyurethane elastomers

which are capable of blocking harmful radiation emitted by various sources are reported.

X-ray shielding capability was generated in the polymer by covalently binding iodine

atoms in a monomer and polymerizing it with other monomers such that the resultant

polymer has the capability of shielding X-radiation. For rendering X-ray shielding

capability to the polyurethane, Bisphenol-A [BPA] was iodinated to 4,4-

isopropylidinedi-[2,6-diiodophenol] [IBPA] and used it as a chain extender during the

synthesis of polyurethane. Polyurethanes were synthesized by reacting 1,6-

Diisocyanatohexane [HDI] and IBPA with two different polyols, namely, poly

[tetramethylene glycol] [PTMG] and poly [hexamethylene carbonate] diol [PHCD]. X-

ray shielding polyurethanes [XPU] were characterized by infrared spectroscopy,

thermogravimetry, dynamic mechanical analysis, energy dispersive X-ray analysis, gel

permeation chromatography and X-radiography. Studies showed that by effectively

changing polyol from polyether to polycarbonate, XPUs having different physico-

mechanical properties could be manufactured. Furthermore, these polyurethanes were

also found to be non-cytotoxic to L929 fibroblast cell lines. X-ray images revealed that

1
incorporation of IBPA has rendered X-ray opacity to the polyurethanes which are several

times higher than aluminium wedge of equivalent thickness. The materials are

sufficiently flexible and rubbery so that it can be used as coatings, films or sheets for

applications in energy sector, power generating nuclear power plants, defense sector

(bunkers for army personnel), medical applications (X-ray diagnostic and CT scanner

rooms, gamma radiation therapy of cancer), etc.

KEYWORDS: X-ray shielding; polyurethanes; 4,4-isopropylidinedi-[2,6-

diiodophenol]; poly [tetramethylene glycol]; poly [hexamethylene carbonate] diol.

INTRODUCTION

Radiation sources are harmful not only for humans but also for sensitive laboratory

equipment. Protection of personnel from radiation is essential in working environments

where X-rays are used. This is important especially in clinical diagnosis, airport

screening areas, in research facilities where production and testing of radiation generating

devices are used, and even in battlefield.[1,2] Furthermore, X-ray shielding polymeric

devices were used in medicine for minimally invasive approaches where X-ray shielding

capability of devices generates images which help the clinician to monitor and control

treatment procedures in real time.[3] It also helps to avoid complications and to assess

therapeutic success detectable by clinically available imaging techniques, like X-ray or

CT imaging. As these imaging techniques generate radiations which can harm those who

are exposed to it, for example, medical radiographic workers, nuclear power plant

operators, soldiers, etc.[46] Use of X-ray shielding materials is of utmost importance to

2
protect these risk groups. X-ray opaque materials can be used for making shields that can

resist radiation penetration. So these materials can act as dual purpose materials for

medical imaging and X-ray shielding applications. Conventionally, X-ray shielding

polymeric formulations are made by adding additives such as lead, barium sulphate,

tungsten or bismuth salts in polymers or by dispersing these additives during the time of

polymerization.[7,8] These inorganic materials are often incompatible with the polymer

matrices and could adversely affect physical and mechanical properties of the polymers.

Polyurethanes have found many medical and industrial applications such as total artificial

heart, heart valves, mammary implants, adhesives, aprons, coatings, etc., because of their

properties such as strength, abrasion resistance and ease of handling favor these

applications.[915] Through the selection of appropriate diisocyanates and diols

polyurethanes with a wide range of physical properties can be produced.[16] For example,

it is possible to synthesize polyurethanes having properties typical of soft elastomers to

those of hard plastics, simply by varying the dominant diol and it will be advantageous if

they exhibit X-ray shielding properties. Incorporating iodine containing moieties in the

polymer chain is an excellent approach to impart X-ray shielding property to

polymers.[1728] Iodine is preferred to impart X-ray opacity for two reasons. Firstly the

greater mass attenuation coefficient of iodine atom, and secondly iodinated compounds

are well accepted as the X-ray opacifying agents of modern nonionic X-ray contrast

media. Since X-ray opacity is a function of iodine content, higher contents of iodine in

the polymer matrix would increase X-ray opacity which will aid effective X-ray shielding

and diagnosis. Studies have shown that a superior approach to impart X-ray opacity to

3
polyurethanes is by incorporating iodinated chain extenders in polymer chain during

synthesis rather than grafting iodine containing compounds later. It may be noted that

grafting technique would be effective only if the polymer possesses sufficient reactive

functional group to which the X-ray opacifying molecule can be attached.[17,18] Even

though, the incorporation of iodinated chain extender is considered as the best option for

imparting X-ray opacity to polyurethanes, this method was found to be more effective in

the case of aromatic diisocyanate based polyurethanes.[2932] Literature reveals that up to

10-15% iodine content could be achieved with aliphatic diisocyanates.[33,34]

In this paper, synthesis and characterization of two melt processable polyurethane

thermoplastic elastomers having improved inherent X-ray shielding capability have been

described. The effect of soft segment chemistry on the physico-chemical and mechanical

properties of the resultant polymers has been evaluated. The technique adopted to

synthesize X-ray shielding polyurethane was to incorporate an iodinated molecule as a

chain extender during polyurethane synthesis.

MATERIALS AND METHODS

Materials

Monomers, namely, Bisphenol-A [i.e., 4,4-isopropylidenediphenol] [BPA] [Sigma-

Aldrich, MO, USA], and 1,6-Diisocyanatohexane [HDI] [SigmaAldrich, MO, USA]

were used without further purification. Polytetramethylene glycol [PTMG] [Terathane

1000 polyether glycol] of Mn=1000 g/mol and Poly[hexamethylene carbonate]diol

[PHCD] of Mn= 860 g/mol [SigmaAldrich, MO, USA] were degassed for 24 h at 50C

4
under reduced pressure. Iodine monochloride, and Dimethyl formamide specially dried

[DMF] were obtained from Merck Chemicals, Mumbai, India. Glacial acetic acid was

procured from S.D Fine Chemicals, Mumbai, India.

Synthesis Of 4,4-Isopropylidinedi[2,6-Diiodophenol] [IBPA]

Iodination of BPA was carried out using Iodine monochloride [ICl] at 70C in glacial

acetic acid. For this, 0.023 mol bisphenol-A was added to 100 ml 12.5% glacial acetic

acid and temperature was raised to 70C to dissolve BPA in the medium. Added 21.38g

[0.13 mol] iodine monochloride [BPA to ICl mole ratio was 1:6], into a beaker and

diluted it with 100mL 25% glacial acetic acid. The ICl solution was added to BPA

solution and stirred for 15 min. The reaction temperature was raised to 90C and stirred

for one hour and then transferred into to 1 liter beaker and allowed to cool. The solidified

mixture was treated with glacial acetic acid to remove the dark mother liquor and dried.

1
HNMR IBPA [300 MHz, DMSO-d6] [ppm]: 1.5 ppm [s, 6H], 7.4 ppm [s, 4H]. 9.4 ppm

[s, 2H, OH]. 13CNMR of IBPA [400 MHz, DMSO-d6] [ppm]: 153.9[C1X2],

146.1[C2X2], 137.5[C3X4], 87.6[C4X4], 40.9[C5X1], 30.6[C6X2].

Synthesis And Characterization Of X-Ray Shielding Polyurethanes

Polyurethanes were synthesized by reacting diisocyanate, polyol and chain extender

taken in the molar ratio 2.2:1.2:1. Polymerization was carried out in a two-step process.

In the first step diisocyanate and diol, both dissolved in DMF, were allowed to react for

4h at 90C to form pre-polymer. Pre-polymer synthesis was carried out in nitrogen

5
atmosphere. In the second step the catalyst, dibutyltin dilaurate [DBTL, 0.05 wt % of

reactants], was added followed by IBPA dissolved in DMF through a pressure equalizer

and the reaction was maintained at 90 C for another 4 h under stirring. After this, the

reaction mixture was allowed to cool to room temperature and kept under stirring for

another 16 h. Polyurethanes formed were isolated by precipitation by adding the reaction

mixture into cold water. The precipitated polymer was further purified by washing with

methanol. The polymer obtained was cast into 1mm thick films by dissolving it in DMF

and samples were dried at 70C in an air oven. The yield obtained for both polyurethanes

was about 90%. Polyurethane obtained by reacting monomers HDI/PTMG/IBPA was

termed XPU1 and that from monomers HDI/PHCD/IBPA was termed XPU2.

CHARACTERIZATION

Infrared [IR] spectra were recorded in a Fourier transform infrared [FTIR] instrument

[Nicolet, model Impact 410, Madison, WI]. NMR spectra were recorded using a Bruker

300 MHz instrument [Bruker AC-300, USA] with TMS as the internal standard and

DMSO d6 as the solvent. Contact angle measurements were done using the sessile drop

method by a video based contact angle measuring device (Data physics OCA 15 plus,

Germany) and imaging software (SCA 20). 3l of liquid water droplet was used at room

temperature (232C) for measurement. XRD analyses were carried out with Siemens D-

5005 diffractometer, using

Cu K radiation at an operating voltage of 40 KV, 30 mA current and a 2 range of 10

to 90. Thermogravimetric analysis [TGA] was carried out using instrument model SDT-

6
2960 [TA Instruments Inc., USA,] in nitrogen atmosphere at a heating rate of 10 C/min.

Molecular weights [ M n and Mw ] and molecular weight distribution were determined by

GPC using a Waters HPLC system with 510 pump, 7725 Rheodyne injector, Styragel HR

columns, Millennium 32 software and R401 Differential refractometer. Tetrahydrofuran

was used as mobile phase at a flow rate of 1mL/min. The instrument was calibrated using

polystyrene standards [Polysciences, Warrington, PA, USA]. Elemental analysis of

iodine was performed by service Central dAnalyse, Centre National de la Recherche

Scientifique, Verniason, France. Energy dispersive X-ray (EDX) analysis was carried out

using Quanta 200 [Environmental SEM] FEI Company, Netherlands. Dynamic

mechanical analysis [DMA] was carried out using Tritec 2000B DMA [Triton

Technology Limited, UK]. Mechanical properties of the XPUs were determined using a

universal testing machine (Instron, model 3345) connected with long travel extensometer.

Cast samples were cut using ISO 527-2 type 5A die and tested at 25oC at a cross-head

speed of 100mm/min. The mean of 6 specimens and their standard deviation were

recorded.

X-ray radiographs were obtained using a standard a Seimens powermobile C arm

fluoroscopy machine under digital radiography (DR) mode (General Electric, USA)

equipped with 2.5mm Aluminium filtration set at 45 kV with 10 mA current for 0.2s. A

quantitative analysis was conducted to determine the extent of X-ray opacity with respect

to controls by means of Image J 1.44 software (National Institutes of Health, US). Test

samples were cut from molded sheets into discs (thickness 0.2mm) and the X-ray image

of the discs was recorded along with the controls. Two types of controls were used: one

7
was an Aluminum wedge with thickness (0.5mm-3mm) increasing on increments of

0.5mm and the other was a non-iodinated commercial polyurethane (Tecophilic H3-93A,

M/s. Lubrizol Corporation, Cleveland, USA) filled with different percentages of BaSO4

(10 to 30% by wt) in a Plastograph (M/s. Brabender GmbH, Germany) by adopting

standard compounding technique. The compounds thus obtained were compression

molded into discs of thickness 0.2 mm. Quantitative measurements were made from the

intensity of the images obtained. For this, the difference between the X-ray radiographic

images of the test sample and the background were measured in terms of pixel intensity

(gray scale value ranging from 0 to 255) and compared with that of controls against the

background. Opacity values caused by controls were calculated using Image J 1.44

software.

In vitro cell culture cytotoxicity of XPU samples was analyzed quantitatively by direct

contact method using L929 fibroblast cells as per the method given in ISO 10993-5

standard and further cytotoxicity of XPUs were quantitatively assessed using MTT assay

as mentioned elsewhere [33].

DATA ANALYSIS

At least three samples were used for all the experiments. Statistical analysis was carried

out using a one-way analysis of variance with 95% confidence intervals. The error bars

denote SD (n 3).

RESULTS AND DISCUSSION

8
The development of X-ray shielding materials were carried out by increasing the overall

electron density of polymers and without the addition of X-ray shielding filler materials.

Filler additives could affect the physical and mechanical properties of the polymers

adversely. Fillers increase the stiffness and density of the materials at the cost of

toughness and light weight. The method adopted for the iodination of BPA was to react it

with iodine monochloride taken in glacial acetic acid. The compound underwent tetra-

iodination and termed IBPA. 1HNMR and 13CNMR analysis confirmed that the reaction

resulted in tetra iodination of BPA (Figures 1 and 2). Studies indicated that mono- or di-

iodinated chain extenders are effective in imparting sufficient X-ray opacity to the

polymer. However, when thin devices are fabricated from these materials, the shielding

capability to X-rays may not be sufficient. Tetra-iodination would be an attractive option

in such cases. So a tetra-iodinated molecule, IBPA, was synthesized and incorporated as

chain extender into the polyurethane chain. Since IBPA has 4 iodine atoms per molecule,

polyurethanes synthesized using this molecule was expected to exhibit sufficient X-ray

shielding capability. To understand the effect of polyols on the overall properties of

polyurethanes, polycarbonate and polyether based polyurethanes were synthesized using

HDI, two polyols (PHCD and PTMG) and IBPA as chain extender (Scheme 1). HDI was

used as one of the monomers since it exhibited excellent light stability, hydrolysis

resistance and lower toxicity compared to those polyurethanes based on aromatic

diisocyanates.[35] The polyurethane obtained by reacting HDI, PTMG and IBPA was

designated as XPU1 and that obtained from HDI, PHCD and IBPA as XPU2.

9
IR spectra of polyurethanes XPU1 and XPU2 are showed in Figure 3. Some of the typical

bands of polyurethanes can be seen in the spectra and the spectral assignments of XPU1

and XPU2 are listed in Table 1. All the characteristic absorptions obtained were typical

of polyurethanes indicating that the polymers formed were indeed iodinated

polyurethanes. Absorption bands in the carbonyl and N-H stretching in the IR spectra

indicated the presence of hydrogen bonds. Micro-phase separation is usually obtained for

phase separable polyurethanes prepared in solution under homogeneous conditions. The

presence of hydrogen bonded carbonyl absorption peak, (1690 cm-1 and 1722 cm-1) in

HDI based polyurethanes revealed the inter urethane hydrogen bonding of the hard

segment domains which may lead to a higher degree of micro-phase separation in the

surface [33]. The absence of the band at 2270 cm-1 indicates the absence of unreacted free

isocyanate in the polyurethanes synthesised. All the synthesized polyurethanes were

linear polymers. Furthermore, none of the polymers showed peaks for allophanate

linkages due to crosslinking. Allophanates are formed due to the reaction between free

isocyanates and the initial urethane bonds formed during the pre-polymer stage of

polyurethane synthesis when the isocyanate index is high. Allophanate linkages are

normally characterized by a triplet of intense IR bands centred at 1220, 1280 and 1310

cm-1 as well as unique N-H absorption peaks at 3298, 3267 and 3233 cm-1.[36] The

absence of these characteristic bands in the IR spectra of these polyurethanes indicated

that undesirable side reactions had not occurred during their syntheses.

EDX analysis shows peaks in the range 3.5 - 4.5 keV confirming the presence of iodine

in XPUs (Figure 4). Quantitative elemental analysis revealed that the iodine content in

10
XPU1 and XPU2 were about 20% which is sufficient for visibility under normal X-ray

operating conditions. This value is much higher than previously reported results with

aliphatic HDI based polyurethanes.[33,34] The most significant attribute of iodinated X-ray

shielding polymers is their iodine content. The relatively high atomic weight of iodine

provides effective X-ray shielding.

Contact angle measurement gives an idea on the effect of polyols on the hydrophobic /

hydrophilic balance of the polymer formed. The contact angle of XPU1 was 1024

whereas that of XPU2 was 853. The decrease in contact angle observed in the case of

XPU2 was due to the influence of polar functionalities in PHCD chains carbonate

linkages. XRD analysis was carried out to verify if crystallinity was introduced into the

polyurethanes by polyols. Segmented polyurethanes consist of alternating hard and soft

chain segments. Microphase separation of these two chemically distinct components may

have strong effect on the physical and mechanical properties of polyurethanes.[3741]

Studies have shown that the reason behind the phase separation into hard and soft

domains is segmental mobility and strong hydrogen bonding.[42] X-ray diffraction

patterns of both XPU1 and XPU2 showed two major peaks, a broad one at 2 = 20 and a

sharp peak at 2 = 28.5 indicating partially crystalline character (Figure 5). The peak at

2 = 20 in polyurethanes corresponds to PTMG/PHCD lattice and the other peak at 2 =

28.5 is due to the interaction of hard segments.[43] IR studies further indicate that the

XPUs are semi-crystalline in nature. For example, IR absorption of urethane carbonyl at

1690 cm1 (which is due to the inter urethane hydrogen bonding of the hard segment

domains) indicate a higher degree of microphase separation. Furthermore, hydrogen

11
bonding between ether/carbonyl groups of the soft segments and the urethane amide in

the hard segments can also take place and such segmental interactions can lead to phase

segregation and broad peaks in XRD spectra.

In order to manufacture products or devices from polymeric materials, they have to be

heated, melted and shaped using polymer processing machines. So it is important to

know the melt processing window and at what temperature the degradation of the

material would start. The thermal stability and processing window of polyurethanes were

determined by using TGA method. TGA result shows that XPU1 and XPU2 are stable up

to 190oC and 185C, respectively (Figure 6). These results indicate that polyurethanes are

stable enough to be processed by molding processes such as injection or extrusion below

these temperatures. The weight average molecular weights determined by GPC revealed

that their weight average molecular weights were also close to each other and were 24300

g/mol and 25800 g/mol, respectively.

Storage modulus and tan delta values are plotted as a function of temperature in Figure 7.

Results showed that the diol controls the properties of the resultant XPUs substantially.

The temperature associated with the peak magnitude of tan is defined as the glass

transition temperature (Tg). When PTMG was used as diol, Tg was observed at -33.5 C

whereas with PHCD the Tg was shifted to a higher temperature, i.e., to -2.9 C. Storage

modulus of the polyurethane also increased by two orders of magnitude when PTMG was

replaced by PHCD. Storage modulus values at different temperatures are listed in Table 2

for comparison. This difference in glass transition temperature and storage moduli is

12
attributed to the relatively greater flexibility of the polyether soft segment of PTMG

compared to the polycarbonate soft segment of PHCD. Furthermore, XPU1 showed

lower tan peak heights than that of XPU2, indicating increasingly elastic behavior of

polyether soft segment. Results indicated that polyurethanes of different Tg and moduli

could be prepared by using polyols of different chain stiffness. Mechanical properties of

XPUs at room temperature showed that their properties were close to each other (Table

3). This is expected as the Tg of the polyurethanes are well below room temperature.

When these polyurethanes are considered for biomedical applications, their safety and

non-toxic nature have to be demonstrated. Therefore, in vitro cytotoxicity of these

polyurethanes was evaluated by two ways using L929 cells: (1) by direct contact assay

and (2) by a MTT viability assay. In vitro cell culture cytotoxicity studies of XPUs

conducted in direct contact method revealed that XPU1 and XPU2 are non-cytotoxic to

L929 mouse fibroblast cell lines. The cellular morphological features are shown in Figure

8. The cells retained their original morphology even after 72 h contact with the materials.

The quantitative cell viability studies by the MTT assay showed that 94% of the cells

were active when they were treated with the extract of XPU1 whereas 91% metabolic

activity was observed in the case of XPU2 (Figure 9).

In order to understand the X-ray proofing property of these materials, XPU1 and XPU2

were subjected to X-radiography (Figure 10).[44] It can be clearly seen that the images

corresponding to XPU1 and XPU2 were substantially darker than the image of

aluminium wedge of equal thickness. Quantitative evaluation of X-ray shielding

13
capability was attempted by analyzing pixel intensity of X-ray radiographic images gray

scale value ranging from 0 to 255.[45] Results of quantitative evaluation of X-ray opacity

made by Image J 1.44 software are shown in Figures 11 and 12. X-ray images reveal that

XPU1 and XPU2 have excellent X-ray opacity and could be easily seen under

fluoroscopy. Results revealed that HDI based XPUs of 200micron thickness have same

X-ray opacity as that of 0.53 - 0.54mm thick aluminum wedge and equivalent X-ray

opacity as that of 21% BaSO4 filled polyurethane. These results reveal that by

incorporating higher concentration of iodine, X-ray opacity of the polymeric materials

can be improved substantially. Furthermore, by manipulating the thickness of XPUs we

can have different extends of X-ray proofing capability for applications in energy sector,

power generating nuclear power plants, defense sector (bunkers for army personnel),

medical applications (X-ray diagnostic and CT scanner rooms, gamma radiation therapy

of cancer), etc.

CONCLUSION

The results of this study have led to the development of additive free, flexible, melt

processable and X-ray shielding polyurethane materials by the incorporation of IBPA

monomer as chain extender. This study also indicates that polyurethanes having different

soft segment chemistries would lead to X-ray proofing materials of widely different

storage moduli, glass transition temperatures, hydrophobic or hydrophilic nature. These

unique properties allow them to be used as molded materials, coatings, etc. in potential

applications that require light weight and radiation shielding capability. These additive

free polyurethanes are recyclable and safe for non-hazardous disposal and are excellent

14
for long procedures. Furthermore, because of their excellent cytocompatibility along with

X-ray shielding capability they are expected to find many biomedical applications such as

interventional and diagnostic medicine, where X-ray opacity is an important concern.

ACKNOWLEDGEMENT

S. Kiran acknowledges the receipt of a senior research fellowship from CSIR-New Delhi,

India. The authors wish to thank the Director, SCTIMST for the laboratory facilities

provided and the kind permission to publish this work.

REFERENCES

1. Smith, D.M. 1998. Radiation shielding. US Patent 7274031.

2. Lange, W. 2003. Method for manufacturing a radiation shielding material. US Patent

6548570.

3. Silberman-Hazony, R. 1988. Encyclopedia of polymer science and engineering. 2nd

ed., New York: Wiley. 14:1-8.

4. Scuderi, G. J. Brusovanik G. V, Campbell D. R, Henry R. P, Kwon B and Vaccaro A.

R. 2006. Evaluation of nonlead-based protective radiological material in spinal surgery.

The Spine Journal 6:577-582.

5. Sheehy, D. M, 1998. X-ray radiation protector for reproductive systems.US Patent

5778888.

6. DeMeo. R. and Kucherovsky, J. 2004. Lightweight radiation protective articles and

methods for making them. US Patent, 6828578.

7. Goldestein, J. A. 2002. Radiation protection system. US Patent, 6448571

15
8. Tomita, Y. H., Nishikawa, H. T. and Haruta Y. K. 2004. Radiation shielding address.

US Patent, 0029998.

9. Szycher, M., Siciliano, A. A. and Reed, A. M. 1994. Polyurethane elastomers in

medicine. In: Dumitriu S, ed. PolymericBiomaterials. New York: Marcel Dekker, pp 233-

244.

10. Lelah, M. D. and Cooper, S. L. 1986 Polyurethanes in medicine. Boca Raton, FL:

CRC Press.

11. Chenguo, L., Suqing, L., Jingbo, Z., Zhiyuan, Z., Junying, Z. and Wantai Y. 2014.

Synthesis and characterization of aliphatic (polyamide urethane)s having different nylon

6 segments through non-isocyanate route. J Polym Res 21:498-452.

12. Violeta, O. P., Emil, B. and Stefan, O. 2013. Dielectric behavior of polyurethane and

polyurethane-urea elastomers with pyridine moieties in the main chain. J Polym Res

20:237-240.

13. Roseany, V. V. L, Nuno, P. D. L, Ana, P. T. P, Ana, C. M. G, Ines, S. R. and Maria,

J. A. S. 2013. Synthesis of polyols and polyurethanes from vegetable oilskinetic and

characterization. J Polym Res 20:238-244.

14. Kai-Jay, C., Yen-Zen, W., Kuan-Chen P., Huang-Shian, T., Jia-Ru, C., Ching-Tang.

H., Ko-Shan, H. and Wan-Fu, L. 2014. Preparation of silica aerogel/polyurethane

composites for the application of thermal insulation. J Polym Res 21:338-344.

15. Tatiana, K., Mrcia, V. G. A., Joao, V. F. V., Thiago, A. S., Luiz, P. R. and Sonia, F.

Z. 2012. Synthesis of new carbohydrate-based polyurethanes and their application in the

purification of methyl esters (biodiesel) J Polym Res 20:48-53

16
16. Shoubing, C., Qihua, W. and Tingmei, W. 2012 Preparation, tensile, damping and

thermal properties of polyurethanes based on various structural polymer polyols: effects

of composition and isocyanate index. J Polym Res 19:9994-9998.

17. James, N. R., and Jayakrishnan, A. 2006 Polyurethanes with radiopaque properties.

Biomaterials 27:160-166.

18. James N. R. and Jayakrishna, A. 2007 On imparting radiopacity to a poly(urethane

urea). Biomaterials 28:3182-3187.

19. Dawlee, S., Jayakrishnan A, and Jayabalan, M. 2008 Studies on novel radiopaque

methylmethacrylate: glycidyl methacrylate based polymer for biomedical applications. J

Mater Sci: Mater Med 20:S243-50.

20. Boelen, E. J. H., Lewis, G., Xu, J., Slots, T., Koole, L. H. and van Hooy-Corstjens, C.

S. J. 2008. Evaluation of a highly-radiopaque iodine-containing acrylic bone cement for

use in augmentation of vertebral compression fractures. J Biomed. Mater. Res 86A:76-

88.

21. Carbone, A. L., Song, M. and Uhrich, K. E. 2008. Iodinated Salicylate-Based

Poly(anhydride-esters) as Radiopaque Biomaterials. Biomacromolecules 9:1604-1612.

22. Mawad, D., Poole-Warren, L. A., Martens, P., Koole, L. H., Slots, T. L. B. and van

Hooy-Corstjens, C. S. J. 2008. Synthesis and characterization of radiopaque iodine-

containing degradable PVA hydrogels. Biomacromolecules 9:263-268.

23. Bergknut, N., Smolders, L.A., Koole, L. H., Voorhout, G., Hagman, R. E.,

Lagerstedt, A., Saralidze, K., Hazewinkel, H. A. W, van der Veen, A. J. and Meij, B. P.

2010. The performance of a hydrogel nucleus pulposus prosthesis in an ex vivo canine

model. Biomaterials 31:6782-6788.

17
24. Mawad, D., Poole-Warren, L. A., Martens, P., Koole, L. H., Slots, T. L. B and van

Hooy-Corstjens, C. S. J. 2008. Synthesis and characterization of radiopaque iodine-

containing degradable PVA hydrogels. Biomacromolecules 9:263268.

25. Hork, D., Metalov, M., Svec, F., Drobnk, J., Klal, J., Borovicka, M., Adamyan,

A. A, Voronkova, O. S. and Gumargalieva, K. Z. 1987. Hydrogels in endovascular

embolization. III Radiopaque spherical particles, their preparation and properties.

Biomaterials 8:142145.

26. Jayakrishnan, A., Thanoo, B. C., Rathinam, K. and Mohanty, M. 1990. Preparation

and evaluation of radiopaque hydrogel microspheres based on PHEMA/iothalamic acid

and PHEMA/iopanoic acid as particulate emboli. J. Biomed. Mater. Res. 24:9931004.

27. Mottu, F., Rfenacht, D. A., Laurent, A. and Doelker, E. 2002. Iodine-containing

cellulose mixed esters as radiopaque polymers for direct embolization of cerebral

aneurysms and arteriovenous malformations. Biomaterials 23:121131.

28. Mawad, D., Mouaziz, H., Penciu, A., Mhier, H., Fenet, B., Fessi, H. and Chevalier,

Y. 2009. Elaboration of radiopaque iodinated nanoparticles for in situ control of local

drug delivery. Biomaterials 30:56675674.

29. Kiran, S., James, N. R., Joseph, R. and Jayakrishnan, A. 2009. Synthesis and

characterization of iodinated polyurethane with inherent radiopacity. Biomaterials

30:5552-5559.

30. Kiran, S., James, N. R., Jayakrishnan, A. and Joseph, R. 2012. Polyurethane

thermoplastic elastomers with inherent radiopacity for biomedical applications. J Biomed

Mater Res A 100A: 34723479.

18
31. Qu,W., Xia, W., Feng, C., Tuo, X. and Qiu, T. 2011. Synthesis and characterization

of radiopaque poly(ether urethane) with iodine-Containing diol as chain extender. J

Polym Sci Part A: Polym Chem 49:21912198.

32. Sang, L., Wei, Z., Liu, K., Wang, X., Song, K., Wang, H. and Qi, M. 2013.

Biodegradable radiopaque iodinated poly(ester urethane)s containing poly(-

caprolactone) blocks: Synthesis, characterization, and biocompatibility J Biomed Mater

Res A. 102:11211130.

33. Dawlee, S. and Jayabalan, M. 2011. Development of segmented polyurethane

elastomers with low iodine content exhibiting radiopacity and blood compatibility.

Biomed Mater 6:055002.

34. Kiran, S. and Joseph, R. 2013. Synthesis and characterization of a noncytotoxic, X-

ray opaque polyurethane containing iodinated hydroquinone bis(2-hydroxyethyl) ether as

chain extender for biomedical applications. J Biomed Mater Res A. 102:32073215.

35. Santerrea, J. P., Woodhouse, K., Laroched, G. and Labow, R. S. 2005. Understanding

the biodegradation of polyurethanes: From classical implants to tissue engineering

materials. Biomaterials 26:7457-7470.

36. Stovbun, E., Kuzaev, A. and Baturin, S. 1996. Allophanate formation in

oligodienediol-aromatic diisocyanate system. Polymer science. Series A, Chemistry,

physics 38(7):691-695

37. Yilgor, I., Yilgor, E., Guler, G., Ward, T. C. and Wilkes, G. L. 2006 FTIR

investigation of the influence of diisocyanate symmetry on the morphology development

in model segmented polyurethanes Polymer 47:4105-4114.

19
38. Da-Kong, L., Hong-Bing T. and Stanford J. L. 1996. Phase separation in segmented

polyurethanes derived from mixtures of polyether polyols with different functionality J

Polym Res 3:221-225.

39. Kung, L., Show-An, C., Yu, T. L. Tsang-Lang, L., Chih-Hao, L., Ji-Jung, K., Szu-Li,

C. and Lin J. S. A small-angle X-ray scattering study of microphase separation transition

of polyurethanes: Effect of hard segments 1995. J Polym Res 2:63-70

40. Xin, L., Jue, C. and Junying, Z. 2014. Preparation of thermal plastic polyurethane-

polystyrene block copolymer via UV irradiation polymerization J Polym Res 21:544-549.

41. Zhendong, S. 2012. Preparation and characterization of high-strength elastomers with

high poly(trifluoropropylmethyl)siloxane content into polyurethane urea J Polym Res

20:57-61

42. Da-Kong, L., Hong-Bing, T. and Standford, J. L. 1996. Phase separation and phase

inversion of polyurethane networks. J Polym Res 3:159-163

43. Mallakpour, S. and Rafiemanzelat, F. 2008. Synthesis, characterization and properties

of a series of copoly (amide-imide-ether-urethane)s with a new hard segment constituent:

study of the effect of hard segment content. High Performance Polymers 20(2):146-165

44. F04 Committee, Test Methods for Determining Radiopacity for Medical Use, ASTM

International, 2007

45. Cortecchia, E., Pacilli, A., Pasquinelli, G. and Scandola, M. 2010. Biocompatible

Two-Layer Tantalum/Titania-Polymer Hybrid Coating. Biomacromolecules 11:2446-

2453

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Table 1. IR spectrum of XPU1 and XPU2

XPU1 XPU2 Peak assignment

3320 cm-1 3318 cm-1 N-H bonded stretching

2931 cm-1 2931 cm-1 C-H asymmetric stretching

2853 cm-1 2855 cm-1 C-H symmetric stretching

1690 cm-1 1739 cm-1 C=O bonded stretching

1535 cm-1 1536 cm-1 N-H bending + C-N stretching

1251 cm-1 1242 cm-1 -C-O-C stretching in O=C-O-C-

1102 cm-1 - C-O-C stretching

21
Table 2. Dynamic mechanical analysis data of XPU1& XPU2

Polymer Storage Modulus [MPa] at: Glass transition

-50oC 0oC 25oC 37C Temperature [Tg]

XPU1 58 1.1 0.6 0.45 -33.5C

XPU2 1890 99.7 33.9 28.6 -2.9C

22
Table 3. Mechanical properties of XPU1 and XPU2

Polyurethane ID Tensile strength Elongation at Toughness /MPa

/MPa break /%

XPU1 5.23 0.23 713 9 25.46 2.17

XPU2 6.14 0.13 560 4 27.12 3.15

23
Scheme 1. Synthesis of X-ray opaque polyurethanes.

24
Figure 1. 1H NMR of IBPA.

25
Figure 2. 13C NMR of IBPA.

26
Figure 3. IR spectrum of XPU1 and XPU2.

27
Figure 4. EDX spectrum of XPU1and XPU2.

28
Figure 5. X-ray diffraction patterns of the polyurethanes XPU1 and XPU2.

29
Figure 6. Thermogravimetric traces of XPU1 and XPU2.

30
Figure 7. Effect of polyol on the storage modulus and tan delta of polyurethane.

31
Figure 8. Optical microscope images of L929 cells grown in vitro on: (A) XPU1 and (B)

XPU2.

32
Figure 9. Quantitative estimation of cell viability on XPU1 and XPU2 by the MTT assay

in comparison with negative control (high density polyethylene-PE) and positive control

(copper wire).

33
Figure 10. X-ray images 200micron thick XPU discs compared with aluminium step-
wedge of thickness ranged from 0.5mm-3mm having incremental steps of 0.5mm
thickness (left to right) and also with10-30% BaSO4 filled polyurethanes disc of 200
micron thickness.

34
Figure 11. X-ray opacity values, reported as relative pixel intensity calculated from a

digitalized X-ray radiographic image, as a function of sample thickness: for aluminum

wedge and for XPU disc. The extent of X-ray opacity of XPU discs is shown marked in

the X-Y plot. (n=3 for each group; Error bars represent the standard deviation of mean).

35
Figure 12. X-ray opacity values, reported as relative pixel intensity calculated from a

digitalized X-ray radiographic image, as a function of different percentages of BaSO4

filled polyurethane. The extent of X-ray opacity of XPU discs is shown marked in the X-

Y plot. (n=3 for each group; Error bars represent the standard deviation of mean).

36